CN102276857A - Preparation method of micron-sized hydroxyapatite-chitosan composite membrane - Google Patents
Preparation method of micron-sized hydroxyapatite-chitosan composite membrane Download PDFInfo
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- CN102276857A CN102276857A CN 201110204259 CN201110204259A CN102276857A CN 102276857 A CN102276857 A CN 102276857A CN 201110204259 CN201110204259 CN 201110204259 CN 201110204259 A CN201110204259 A CN 201110204259A CN 102276857 A CN102276857 A CN 102276857A
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Abstract
The invention belongs to the field of biomedical engineering and relates to a preparation method of micron-sized hydroxyapatite-chitosan composite membrane. The preparation method comprises the following steps of: degreasing and deproteinizing porcine cancellous bone serving as a raw material; calcining and performing ball milling to prepare micron-sized hydroxyapatite; ultrasonically dispersing the micron-sized hydroxyapatite into deionized water, mixing with acetic acid solution of chitosan; and preparing the micron-sized hydroxyapatite-chitosan composite membrane by a curtain coating solvent volatilization method. In the micron-sized hydroxyapatite-chitosan composite membrane prepared by the method, the micron-sized hydroxyapatite is dispersed into the chitosan uniformly; and osteogenic precursor cells MC3T3-E1 can be adhered to the composite membrane and can proliferate on the composite membrane.
Description
Technical field
The present invention relates to a kind of preparation method of micron order hydroxyapatite-chitosan complex film, be to be raw material specifically with the pig spongy bone, become the micron order hydroxyapatite through Processing of Preparation such as calcining ball millings, prepare composite membrane with chitosan blend again, belong to biomedical engineering field.
Background technology
Hydroxyapatite is the main moiety of inorganics in the bone, has excellent biological compatibility, in bone grafting material and bone tissue engineering stent material, is widely used because of having bone conduction effect with the very strong Chemical bond of bone forming.The main component of forging bone is a hydroxyapatite, and it has eliminated the immunogenicity of heterogeneity biological bone fully, and the structural similitude of hole and spongy bone has the traffic between the good Kong Yukong, helps growing into of scleroblast, blood vessel, based on direct skeletonization.Yet the fragility of single hydroxyapatite under physiological environment and low fatigue strength have limited it and have used in load sending down the fishbone reparation or bone alternate, and the compound one deck macromolecular material of forging bone pore surface for preparing can be improved its over-all properties.With hydroxyapatite and thereby medical macromolecular materials are compound strengthens toughness and give full play to the hydroxyapatite excellent biological compatibility, be the main direction of studying of hydroxyapatite composite material.
Chitosan is the product that is partly taken off acetyl by the chitin that Crustacean is extracted, because its excellent biological compatibility and degradation property become a kind of natural polysaccharide that is widely used in Tissue Engineering Study.Chitosan is the rare a kind of positively charged alkaline polysaccharide of occurring in nature, is widely used in biomedical sector because of having favorable biological degradability, biocompatibility, nontoxicity, nonirritant.But chitosan lacks bone bonding biological activity, thereby has limited its application in bone tissue engineer.
Summary of the invention
Lack the active shortcoming of bone bonding in order to overcome the fragility of single hydroxyapatite under physiological environment and low fatigue strength and chitosan, the invention provides a kind of method for preparing the composite film material of micron order hydroxyapatite and chitosan.For this reason, the present invention adopts following technical scheme:
A kind of preparation method of micron order hydroxyapatite-chitosan complex film comprises the following steps:
(1) with the spongy bone is raw material, calcines the preparation hydroxyapatite again through the degreasing deproteinated;
(2) utilize ball milling method to prepare the micron order hydroxyapatite;
(3) take by weighing micron order hydroxyapatite and the chitosan of weight proportion between 6: 4 to 3: 7;
(4) micron order hydroxyapatite homogeneous is scattered in the deionized water, mixes with the aqueous acetic acid of chitosan;
(5) prepare micron order hydroxyapatite-chitosan complex film by the curtain coating solvent evaporation method.
As preferred implementation, the Deproteinated method of degreasing is for to be undertaken by hydrogen peroxide and ether circulation immersion, and calcining temperature is 800-1100 ℃; The ball milling method that preparation micron order hydroxyapatite adopts is for to carry out in planetary ball mill, and ball-milling medium is the mixture of different diameter corundum ball, and the diameter of ball is respectively 8mm, 5mm, 3mm; The particle diameter of micron order hydroxyapatite is in the 1-2 mu m range; The micron order hydroxyapatite ultra-sonic dispersion of preparation carries out blend with chitosan.
The invention has the beneficial effects as follows: in order to solve the problem of monoblock forging bone and chitosan interface bond strength difference, the present invention carries out ball milling with forging bone and carries out compound with chitosan again with the particle diameter that reduces hydroxyapatite.Adopt the tensile mechanical properties of composite membrane of method of the present invention preparation better, can reach: rupture stress reaches as high as 6.0MPa, and breaking strain is between 69-130%.Skeletonization precursor cell MC3T3-E1 cell is cultivated on described micron order hydroxyapatite-chitosan complex film, and the result shows that composite membrane of the present invention has the good cell consistency.
Description of drawings
Fig. 1 is the infrared spectrogram of micron order hydroxyapatite.
Fig. 2 is the tensile stress-strain figure of the micron order hydroxyapatite-chitosan complex film of different proportionings, and every curve characterizes a kind of sample of proportioning.
Fig. 3 is the distribution Electronic Speculum figure of micron order hydroxyapatite in chitosan.
Fig. 4 is the Electronic Speculum figure of skeletonization precursor cell MC3T3-E1 after cultivating on micron order hydroxyapatite-chitosan complex film.
Embodiment
Below in conjunction with specific embodiment the present invention is done and to describe in further detail.
Forging bone is to be raw material with the spongy bone among the present invention, process degreasing deproteinated calcining method again is prepared from, the Deproteinated method of degreasing is for to be undertaken by hydrogen peroxide and ether circulation immersion, calcining temperature is 800-1100 ℃, ball milling carries out in planetary ball mill, and adopting the corundum ball is ball-milling medium.The particle diameter of described hydroxyapatite is gone through analyser analysis by laser and is determined in the 1-2 mu m range.
The curtain coating solvent evaporation method was prepared from after the preparation method of composite membrane of the present invention adopted blend.The ratio of micron order hydroxyapatite and chitosan (weight ratio) is 6: 4,5: 5, and 4: 6,3: 7.Micron order hydroxyapatite homogeneous is scattered in the deionized water, mix with the aqueous acetic acid of chitosan the back adopt blend after the curtain coating solvent evaporation method be prepared into composite membrane.The tensile mechanical properties of composite membrane is: rupture stress is in the 1.7-6.0MPa scope, and breaking strain is between 69-130%.
Skeletonization precursor cell MC3T3-E1 cell is cultivated on described micron order hydroxyapatite-chitosan complex film, and the result shows that described composite membrane has the good cell consistency.
Embodiment one
Commercially available pig bone is removed soft tissue, gets the two ends spongy bone, is cut into the thin slice that thickness is about 2mm, hydrogen peroxide and ether circulation degreasing, and deproteinated is cleaned 70 ℃ of dryings.800 ℃ of calcinings, the ball milling parameter is: diameter is that the proportioning of the corundum ball of 8mm, 5mm, 3mm is 4: 4: 2, ball milling speed 170r/min, the ball milling time is 1h, ball milling is after filtration drying makes the micron order hydroxyapatite.Micron order hydroxyapatite ultra-sonic dispersion with preparation carries out blend with chitosan with 6: 4 ratio, prepares micron order hydroxyapatite-chitosan complex film by the curtain coating solvent evaporation method.The distribution of micron order hydroxyapatite in chitosan as shown in Figure 3.
Embodiment two
Commercially available pig bone is removed soft tissue, gets the two ends spongy bone, is cut into the thin slice that thickness is about 2mm, hydrogen peroxide and ether circulation degreasing, and deproteinated is cleaned 70 ℃ of dryings.1000 ℃ of calcinings, the ball milling parameter is: diameter is that the proportioning of the corundum ball of 8mm, 5mm, 3mm is 4: 4: 2, ball milling speed 230r/min, the ball milling time is 2.5h, and ball milling is after filtration drying makes the micron order hydroxyapatite, and its infrared spectrogram is as shown in Figure 1.Micron order hydroxyapatite ultra-sonic dispersion with preparation carries out blend with chitosan with 5: 5 ratio, prepares micron order hydroxyapatite-chitosan complex film by the curtain coating solvent evaporation method.
Embodiment three
Commercially available pig bone is removed soft tissue, gets the two ends spongy bone, is cut into the thin slice that thickness is about 2mm, hydrogen peroxide and ether circulation degreasing, and deproteinated is cleaned 70 ℃ of dryings.800 ℃ of calcinings, the ball milling parameter is: diameter is that the proportioning of the corundum ball of 8mm, 5mm, 3mm is 3: 3: 4, ball milling speed 260r/min, the ball milling time is 2.5h, ball milling is after filtration drying makes the micron order hydroxyapatite.Micron order hydroxyapatite ultra-sonic dispersion with preparation carries out blend with chitosan with 3: 7 ratio, prepares micron order hydroxyapatite-chitosan complex film by the curtain coating solvent evaporation method, and its tensile stress-strain curve as shown in Figure 2.
Embodiment four
Commercially available pig bone is removed soft tissue, gets the two ends spongy bone, is cut into the thin slice that thickness is about 2mm, hydrogen peroxide and ether circulation degreasing, and deproteinated is cleaned 70 ℃ of dryings.1100 ℃ of calcinings, the ball milling parameter is: diameter is that the proportioning of the corundum ball of 8mm, 5mm, 3mm is 4: 3: 3, ball milling speed 230r/min, the ball milling time is 1h, ball milling is after filtration drying makes the micron order hydroxyapatite.Micron order hydroxyapatite ultra-sonic dispersion with preparation carries out blend with chitosan with 3: 7 ratio, prepares micron order hydroxyapatite-chitosan complex film by the curtain coating solvent evaporation method.Inoculation skeletonization precursor cell MC3T3-E1 on composite membrane, the extended configuration of cell on micron order hydroxyapatite-chitosan complex film as shown in Figure 4.
Although in conjunction with the accompanying drawings the present invention has been carried out foregoing description; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; rather than it is restrictive; those skilled in the art is under enlightenment of the present invention; do not break away from many distortion of making under the aim of the present invention, all belonging to the row of protection of the present invention.
Claims (5)
1. the preparation method of a micron order hydroxyapatite-chitosan complex film comprises the following steps:
(1) with the spongy bone is raw material, calcines the preparation hydroxyapatite again through the degreasing deproteinated;
(2) utilize ball milling method to prepare the micron order hydroxyapatite;
(3) take by weighing micron order hydroxyapatite and the chitosan of weight proportion between 6: 4 to 3: 7;
(4) micron order hydroxyapatite homogeneous is scattered in the deionized water, mixes with the aqueous acetic acid of chitosan;
(5) prepare micron order hydroxyapatite-chitosan complex film by the curtain coating solvent evaporation method.
2. the preparation method of micron order hydroxyapatite-chitosan complex film according to claim 1 is characterized in that, the Deproteinated method of degreasing is for to be undertaken by hydrogen peroxide and ether circulation immersion, and calcining temperature is 800-1100 ℃.
3. the preparation method of micron order hydroxyapatite-chitosan complex film according to claim 1 and 2, it is characterized in that, the ball milling method that preparation micron order hydroxyapatite adopts is for to carry out in planetary ball mill, ball-milling medium is the mixture of different diameter corundum ball, and the diameter of ball is respectively 8mm, 5mm, 3mm.
4. according to the preparation method of the described micron order hydroxyapatite-chitosan complex film of claim 1 to 3, it is characterized in that the particle diameter of micron order hydroxyapatite is in the 1-2 mu m range.
5. according to the described micron order hydroxyapatite-chitosan complex film of claim 1 to 3, it is characterized in that the micron order hydroxyapatite ultra-sonic dispersion for preparing carrying out blend with chitosan.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920193A (en) * | 2014-04-04 | 2014-07-16 | 北京大学口腔医院 | Preparation method of bioactive factor loaded bone-like ceramic composite material |
| CN105536066A (en) * | 2016-01-06 | 2016-05-04 | 山东省中医药研究院 | Material of support for treating femoral head necrosis and preparation method thereof |
| CN110585485A (en) * | 2019-10-29 | 2019-12-20 | 湖南师范大学 | Novel bamboo fiber/hydroxyapatite/chitosan composite membrane and preparation method thereof |
| CN112850677A (en) * | 2021-02-05 | 2021-05-28 | 海南热带海洋学院 | Pickering emulsion taking fishbone as raw material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376038A (en) * | 2008-10-07 | 2009-03-04 | 浙江大学 | Method for preparing composite bone repair stent material containing chitosan and hydroxylapatite |
| CN101721744A (en) * | 2008-10-13 | 2010-06-09 | 佳木斯大学 | Method for preparing rhizoma drynariae/pig bone powder/chitosan compound bracket material |
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2011
- 2011-07-21 CN CN 201110204259 patent/CN102276857A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376038A (en) * | 2008-10-07 | 2009-03-04 | 浙江大学 | Method for preparing composite bone repair stent material containing chitosan and hydroxylapatite |
| CN101721744A (en) * | 2008-10-13 | 2010-06-09 | 佳木斯大学 | Method for preparing rhizoma drynariae/pig bone powder/chitosan compound bracket material |
Non-Patent Citations (3)
| Title |
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| 《中国组织工程研究与临床康复》 20091015 Li Zhi-hong等 Characterization of collagen-chitosan/hydroxyapatite composite membrane for guided tissue regeneration 8388-8392 1-5 第13卷, 第42期 * |
| 《动能材料》 20081231 程先苗等 纳米羟基磷灰石/壳聚糖复合膜的制备和表征 983-986 1-5 第39卷, 第6期 * |
| 《生物医学工程学杂志》 20090630 杨菊林等 壳聚糖/羟基磷灰石膜的制备及对细胞生长的影响 580-584 1-5 第26卷, 第3期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920193A (en) * | 2014-04-04 | 2014-07-16 | 北京大学口腔医院 | Preparation method of bioactive factor loaded bone-like ceramic composite material |
| CN103920193B (en) * | 2014-04-04 | 2015-08-05 | 北京大学口腔医院 | The preparation method of the class bone ceramic composite of a kind of year bioactie agent |
| CN105536066A (en) * | 2016-01-06 | 2016-05-04 | 山东省中医药研究院 | Material of support for treating femoral head necrosis and preparation method thereof |
| CN105536066B (en) * | 2016-01-06 | 2018-10-16 | 山东省中医药研究院 | It is a kind of to be used to treat timbering material of caput femoris necrosis and preparation method thereof |
| CN110585485A (en) * | 2019-10-29 | 2019-12-20 | 湖南师范大学 | Novel bamboo fiber/hydroxyapatite/chitosan composite membrane and preparation method thereof |
| CN112850677A (en) * | 2021-02-05 | 2021-05-28 | 海南热带海洋学院 | Pickering emulsion taking fishbone as raw material and preparation method thereof |
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